HU193185B - Process for producing mixture of crystalline /1r,cys/-3-/z-2-chloro-3,3,3-trifluoro-prop-1-en-1-yl/-2,2-dimethyl-cyclopropane-carboxylic acid-/s/-cyano-3-phenoxy-benzyl-ester and /1s,cys/-3-/z-2-chloro-3,3,3-trifluoro-prop-1-en-1-yl/-dimethyl-cyclopropane-carboxylic acid-/r/-alpha-cyano-3-phenoxy-benzyl-ester and insecticide compositions containing them as active agents - Google Patents

Abstract

There is provided a novel crystalline material consisting of on enantiomeric pair of cyhalothrin isomers having greater insecticidal activity than cyhalothrin itself, and a process for obtaining the crystalline material by crystallisation from concentrated cyhalothrin solutions in lower alkanols or liquid alkanes. The crystalline material may be obtained in the form of either the racemic mixture or the racemic compound of the isomer pair.

Description

The present invention relates to a crystalline process comprising cis-3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl. - (1R, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) substantially free of other isomers of cyclopropanecarboxylic acid a-cyano-3-phenoxybenzyl ester ) - 2,2-Dimethylcyclopropanecarboxylic acid (S) -? - cyano-3-phenoxybenzyl ester and (1S, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop) -1-ene-yl) -2,2-dimethylcyclopropanecarboxylic acid (R) -? - cyano-3-phenoxy-benzyl ester in a 1: 1 molar ratio.

Also known as "cyhalothrin" is cis-3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid a-cyano-3 the preparation of phenoxybenzyl ester and its use as an insecticide, inter alia, in U.S. Patent No. 4,183,498. U.S. Pat. The compound described therein is a mixture of the following four isomers:

"A" isomer: ester of (+) - cis-carboxylic acid with a- (S) -alcohol, "B" isomer: ester of (-) - cis-carboxylic acid with a- (R) -alcohol, "C" isomer : ester of (+) - cis-carboxylic acid with a- (R) -alcohol, and the D-isomer: ester of (-) - cis-carboxylic acid with a- (S) -alcohol.

Cyhalothrin usually contains between 40% and 60% by weight of the "A" and "B" isomers and between 60% and 40% by weight of the "C" and "D" isomers. This material is a viscous liquid at room temperature and cannot be crystallized upon cooling.

The "A" and "B" isomers have the same physical properties (e.g., solubility, melting point, etc.); these isomers differ only in the optical rotation direction. The isomers "A" and "B" are thus enantiomeric pairs of each other; similarly ineffective. The "A" isomer is the ebenantiomeric pair, the "C" and "D" isomers.

It is known (Pestic. Sci. Ii / 2 /, 156-164 / 1980 /) that of the four isomers, the "A" isomer has the most potent insecticidal activity, whereas the "B" and "D" isomers in house flies (Musca domestica). (±) -cis / trans-3- (2,2-dichloro-vinyl) -2,2-dimethylcyclopropanecarboxylic acid 3-phenoxybenzyl ester (an insecticide known as permethrin) was used in the experiment. 25 times exhibit stronger insecticidal activity and can be considered one of the most representative of ^the currently known insecticides. Although it would be highly advantageous to use only the "A" isomer as an active ingredient in insecticidal compositions, its practical implementation is difficult because the pure "A" isomer requires optically pure starting acid and alcohol and the starting materials must be reacted under conditions in which the direction of optical rotation of the materials does not change. At present, there are no known 2 syntheses for the preparation of the "A" isomer in pure form without the formation of other isomers, and for the separation of the undesired isomers formed in the process, their conversion and conversion to the desired "A" isomer.

In our experiments, we have developed a new method that can easily separate the enantiomeric pair formed by the "A" and "B" isomers from the enantiomeric pair formed by the "C" and "D" isomers by simple physical method without stereoselective synthesis or chemical resolution. The insecticidal activity of the enantiomeric pair isolated according to the invention exceeds the activity of the mixture of four isomers.

The present invention therefore relates to a process having a crystalline structure, cis-3- (Ζ-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid α-cyano. -3-: (1Rcis) -3- (Z-2-Chloro-3,3,3-trifluoroprop-1-en-1-yl) substantially free of other isomers of the enoxybenzyl ester-2,2- dimethylcyclopropanecarboxylic acid (S) -α-cyano-3-phenoxybenzyl ester and (1S, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl-cyclopropanecarboxylic acid (R) -? - cyano-3-phenoxybenzyl ester in a 1: 1 molar ratio. According to the present invention, the following steps are taken:

(i) (1R, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid (S) - α-cyano-3-phenoxybenzyl ester, (1R-cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2- dimethylcyclopropanecarboxylic acid (R) -α-cyano-3-phenoxybenzyl ester, (1S, cis) -3- (Ζ-2-chloro -3,3,3-trifluoroprop-1-en-1) (iii) -2,2-dimethylcyclopropanecarboxylic acid (S) -α-cyano-3-phenoxybenzyl ester and (1S, cis) -3- (Z-2-chloro-3,3,3- trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid (R) -? - cyano-3-phenoxybenzyl ester with C2-C6 alkanol or C8-C8 liquid alkane. (ii) cooling the solution to -20 ° C to + 10 ° C and adding crystals of the enantiomeric pair to be separated; 0.5 to 25% by weight, preferably 1.0 to 10% by weight, based on the solute, (iii) (ii) separating the precipitated crystalline material from the solution and (v) optionally recrystallizing the resulting crystalline material in one or more steps until the other cis-3- (Z) is present. -2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid? -Cyano-3-phenoxybenzyl ester in an amount of 10% or more by weight does not decrease to a lower value.

The term "substantially free of other isomers" is intended to mean the invention

The product obtained by the process of -2193185 contains up to 10% by weight of other isomers of cyhalothrin.

Preferred alkanol solvents are ethanol, isopropanol, butan-1-ol, butan-2-ol, pentan-1-ol, 1: 1 isopropanol / tert-butanol, 2: 1 isopropanol / 1.2 ethanediol, isopropanol may be used. Suitable liquid alkane solvents are preferably n-hexane or n-heptane.

The cyhalothrin used as starting material in the process of the invention may optionally contain up to 10% by weight of trans isomers and (E) -isomers as impurities. Preferably, the starting material is cyhalothrin of at least 95% by weight, since the desired product is usually obtained in a higher yield and purity.

In the second step of the process according to the invention, crystalline material which can be used as seed crystals may be prepared, for example, by separating the desired enantiomeric pair from the cyhalothrin by high-performance liquid chromatography.

Preferably, the cyhalothrin is dissolved in the solvent, if necessary with gentle heating, then cooled to 0 to 10 ° C and maintained at this temperature for a while. When a relatively large amount of crystalline material has precipitated from the solution, the solution is further cooled to a temperature of -15 ° C to -5 ° C, and the solution is maintained at this temperature until substantially crystallization is complete.

Other product isomers may be removed from the product of the present invention by recrystallization if necessary. Any suitable solvent may be used for recrystallization, for example any solvent used in the preparation of the product.

(IR, -cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid (S) -α- cyano-3-phenoxy-benzyl ester and (1S, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl- cyclopropanecarboxylic acid - (R) a-cyano-3-phenoxybenzyl ester, cis-3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2 2-Dimethylcyclopropanecarboxylic acid a-cyano-3-phenoxybenzyl ester substantially new in enantiomeric pair.

The process according to the invention can be obtained in two different forms; these are hereinafter referred to as "1. product «and» 11. product «. Product I is slowly precipitated from solution and a standstill of at least 7 to 15 days, and sometimes even longer, is preferably required to obtain a satisfactory yield. II. product crystallizes much faster than the previous product and can be isolated in good yields within 1-6 days.

If, in the second step of the process, a pair of separated crystalline enantiomers is added to the solution by high pressure liquid chromatography, product I usually precipitates out of solution. If this product is recrystallized several times and used as inoculum in further crystallization operations, there is an increasing likelihood that the desired enantiomeric pair is II. precipitate out of solution as a product. After several crystallizations, the product was subjected to II. product. If, hereinafter referred to as Annex II. product is used as seed crystal, the desired enantiomeric pair being the solution in each case

II. product.

Product I is a white, crystalline solid, m.p. 36-42 ° C. Removal of the impurity "C" and "D" isomers by recrystallization from product I gives the product as a white crystalline solid, m.p. 41-42 ° C. Infrared data show that product I is a conglomerate of a mixture of crystals, where each individual crystal is either a pure "A" isomer or a pure "B" isomer, and the product contains nearly the same amount of crystals of "A" and "B" isomers. The

Product I is thus a racemic mixture. Product I forms fine needle crystals which, as previously reported, are relatively slow to precipitate even from concentrated cyhalothrin solutions. The product can be filtered relatively slowly because fine needle crystals sometimes clog the filter.

II. product at 47 C for ³ elevated temperature, usually 48-50 ° C melting material. II. product crystallizes at a much faster rate than product I and forms as monoclinic crystals resembling rhomboids. These crystals, unlike fine needle crystals, do not clog the filter. product can be filtered more easily than product I.

II. Infrared spectroscopy and X-ray crystallographic analysis of the product show that each crystal is composed of equal amounts of "A" and "B" isomers, which are arranged in the crystal lattice correctly. Accordingly, Annex II. product is a racemic compound.

II. A crystal of about 0.13X0.13X0.12 mm was subjected to X-ray diffraction. The assay was performed on a Philips PW1100 four-x-ray diffractometer using a graphite monochromator and Mo-K radiation. The assay was performed with a 0 to 20 type scan, with a scan speed of 0.5 s ~ 'and a scan width of 0.8 °. Reflections in the range of 3 ° <0 <25 ° were investigated by the method of K. R. Adam et al., Inorg. Chem. 19, 2956 (1980). This test yielded the following characteristic crystal 1 logographic data:

crystal ore: monoclinic group: C2 / c

-3193185

6 = 34,764 (5), b = 7,023 (2), c = 18,624 (3) Δ β = 101.95 (3) °, U = 4448.46 Ά 3, Z = 8 density: 1.343 g / cm ³ , F (000) = 1856 (Mo-K i = 1.77 cm ¹ , (Mo-K i = 0.71069 A)

The molecules of the "A" and "B" isomers are arranged in the crystal lattice alternately; in the individual molecules, the trifluoromethyl group is in a trans position relative to the cyclopropane ring (i.e., the substance is the Z isomer). The elementary cell contains 4 to 4 molecules of each of the isomers.

No. 4,183,948 of the product of the invention. U.S. Pat.

The insecticidal compositions of the present invention have a crystalline active ingredient, cis-3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid. substantially free of other isomers of cyano-3-phenoxybenzyl ester (1R, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2 dimethylcyclopropanecarboxylic acid (S) -acyano-3-phenoxybenzyl ester and (1S, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en- l-yl) - 2,2-dimethylcyclopropanecarboxylic acid (R) -? - cyano-3-phenoxybenzyl ester in a 1: 1 molar ratio in an amount of 0.0001 to 95% by weight with an inert solid or liquid carrier. or a diluent and optionally one or more known surfactants.

The invention is further illustrated by the following non-limiting examples.

Table 1

In the examples, the 1R, cis-S isomer (the carbon atom of the cyclopropane ring bearing the carboxyl group is in the R configuration, the two hydrogen atoms attached to the cyclopropane ring are in the cis position relative to each other, the carbon atom bearing the cyano group is in the S configuration). The term "isomer" refers to IS, cis-R, the "C" isomer to IR, cis -15-R, and the "D" isomer to 15S, cis-S.

Pete 1

This example illustrates the separation of cis-3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid a- cyano-3-phenoxybenzyl ester isomeric mixture for two enantiomeric pairs.

The material to be separated was subjected to thin layer chromatography using a 0.25 mm thick silica gel plate as an adsorbent and using diethyl ether / n-hexane (Table I) as the eluent. According to the results of this study, the two enantiomeric pairs are not properly separated by this method. Mean Rr values for the two components are shown in Table I below.

Elution Composition (Mean) AR

Diethyl ether: n-hexane: 90 0.22 0.025 15: 85 0.28 0.030 20: 80 0.33

The separation is carried out by high performance liquid chromatography. For the operation, a Waters Associates System 500 equipped with a column packed with PrepPAK — 500 grade silica gel is used. ^'0 of the column with 0.5 g of cyhalothrin is applied, comprising the 1S, cis-S / IR, cis-R and lR-cis-S / lS, cis-R enantiomer pair 55:45 ratio. The eluant was diethyl ether / petroleum ether 1: 9 (boiling range 40-60 ° C) and the flow rate was adjusted to 0.2 L / min. The eluate was collected into fractions after 4 passages. According to NMR spectroscopy, the first fraction contains the IS, cis-θθ -S / 1R, cis-R enantiomeric pair, and the second fraction contains the 1R, cis-S / 1S, cis-R enantiomeric pair. Both fractions are about 98% pure; the amount of isolated material corresponds to about 65 ⁴ % of the starting material. The NMR spectra (chemical shift, δ, in CDCl 3) of the separated enantiomeric pairs are shown in Table II. listed in the table.

II. spreadsheet

IR, cis-S / 1S, cis-R 1S, cis-S / 1R, cis-R

1,211 1, 30J CD) 1.34 (S) 1,98-, 1.987 2.07 2.19 cm) 2.07 2.19 (M) 2.29 2.29 2.38 2.38J 6,38J cs) - ^ 6.32 (S) 6.771 6.87 / (D) 6.771 6.874 CD) 6,97- 7.50 (m) 6,97- -7.50 (m)

-4193185

Example 2

This example describes how to crystallize the enantiomeric pair of 1R, cis-S / 1S, cis-R from a solution of cyhalothrin. The crystals isolated according to Example 1 are used as seed crystals.

455.6 g of cis-3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid a-cyano-3-phenoxy benzyl ester (a mixture of cis-isomers, the mixture of isomers being 43.2% by weight of 1R, cis-S and 1S, cis-R-isomer and 56.8% by weight of 1S, cis-S and 1R.cis- Contains R-isomer) Dissolve in 460 mL of isopropanol distilled from calcium hydride. During dissolution, the mixture is heated to about 50 ° C. The resulting solution was cooled to 3 ° C by magnetic stirring (using a magnet coated with polytetrafluoroethylene) and then cis-3- (Z-2-chloro-3,3,3- trifluoroprop-1-en-1-yl) - 2,2-dimethylcyclopropanecarboxylic acid - cyano-3-phenoxybenzyl ester crystals (mixture of 1R, cis-S and 1S, cis-R isomers) We are added. After stirring for 9 days at 3 ° C, the slurry was cooled to -10 ° C and vigorously stirred for 7 days with a paddle pad coated with polytetrafluoroethylene.

The precipitated solid is filtered off at 3 ° C, dried under suction, washed once with 100 ml petroleum ether (boiling range 40-60 ° C) and dried in a vacuum desiccator to constant weight over phosphorus pentoxide. 97.6 g of white crystals are obtained. Capillary gas / liquid chromatography showed the product to contain 86.9% by weight of a 1: 1 mixture of 1R, cis-S and 1S, cis-R isomers. The resulting solid was dissolved in 300 ml of dry petroleum ether (boiling range 40-50 ° C), cooled to 3 ° C with stirring, and some cis-3- (Z-2-chloro-3.3) was added to the solution. 3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid α-cyano-3-phenoxybenzyl ester seed crystal (mixture of 1R, cis-S and 1S, cis-R isomers) We are added. After 2 hours, the resulting white suspension was filtered at 3 ° C, the solid dried under suction and dried in a vacuum desiccator over phosphorus pentoxide. 73.6 g of a white crystalline material containing 92% by weight of a 1: 1 mixture of 1R, cis-S and 1S, cis-R isomers are obtained. The product melts at 36-42 ° C. After recrystallization, m.p. 41.5-42 ° C is obtained.

Example 3

IR, cis-S isomer, 6.4 g of 1S, cis-R isomer, 3.2 g of 1S, cis-S isomer and 3.2 g of IR, cis-R isomer mixture of cyhalothrin is 20 ml It is dissolved in n-hexane and the solution is stirred at -5 ° C under a nitrogen atmosphere. A few seed crystals were added to the cooled solution (using the seed crystal as a racemic mixture, purified and recrystallized according to Example 2, m.p. 41.5-42.0 ° C), and the mixture was stirred at -5 ° C for 16 hours. . The precipitated solid was filtered through a sintered glass filter cooled to 0 ° C and washed twice with -5 ° C hexane. 9.30 g of material having a purity of at least 99% relative to the cyhalothrin isomers and a 1: 1 ratio of the 1R, cis-S and 15S, cis-R isomers are obtained. containing at least 96.3% by weight.

The product obtained differs from that obtained in Example 2 by infrared spectroscopic analysis. The two products also have different crystal forms; the material prepared in Example 2 is needle-crystalline whereas the product obtained in Example 3 is rhomboid. Thus, the procedure of Example 3 gives a racemic mixture having individual crystals containing the 1R, cis-S and IS, cis-R isomers in a 1: 1 ratio.

Infrared bands (on liquid paraffin-impregnated gauze): 1050, 1030, 1010, 990, 970 (shoulder), 963, 950, 935, 920, 908, 904, 895, 888, 873, 838, 830 (shoulder), 820, 805, 795, 785, 760, 748, 725, 702, 696 and 650 cm -1.

The infrared spectrum of the product of Example 3 is shown in Figure 1, and the product of Example 2 is infrared.

Figure 2, while the infrared spectrum of the pure 1 R, cis-S isomer is shown in Figure 3. It can be seen that the product of Example 2 and the pure IR have the same cis-S-isomer spectrum, thus the product of Example 2 is a conglomerate of crystals of individual isomers. In contrast, the individual crystals of the product of Example 3 contained 1: 1 of each of the isomers, thus forming a racemic compound.

Example 4

Cyhalothrin containing 20.61 g of the "A" isomer, 20.61 g of the "B" isomer, 4.04 g of the "C" isomer and 4.04 g of the "D" isomer are dissolved in 100 ml of warm hexane and the solution is heated to 5 ° C. cool, and add some seed crystals obtained in Example 3 to the solution. The mixture is then cooled slowly to -5 ° C with vigorous stirring.

The precipitate was filtered off, washed with cold hexane and air-dried. 28.6 g of a mixture of 1R-cis-S / 1S, cis-R isomer (racemic compound) are obtained; mp 49-50 ° C.

Example 5

This example describes the isolation of the racemic compound (product II).

Flask containing glass beads in 200 ml of isopropanol 200 g of technical grade (purity 95.8 wt ° / ₀₎ cyhalothrin filled, cooling the solution to -5 ° C, and 4.0 g of crystalline racemic compound added. The mixture was stirred for 23 hours at -5 ° C by rotating the flask. The precipitate formed was cooled

Filter through a sintered glass filter surrounded by a -5193185 handle, cooled to -5 ° C, washed with an equal volume of pre-cooled n-hexane and then dried. 39.5 g of a mixture of 1R, cis-S / 1S, cis-R isomers (racemic compound) are obtained; mp 49.5-50 ° C.

Example 6

This example illustrates how the reaction conditions (solvent quality, kill, table doser to cyhalothrin ratio, reaction time, temperature) affect the purity and yield of the racemic mixture (product I). Starting with 42 ± 1% by weight of cyhalothrin containing 1R, cis-S / 1S, cis-R enantio5 mer, and adding some crystals of the racemic mixture (product I) to the cooled mixture. The reaction conditions and results are shown in Table III. in Table.

The Compound- The Cyhalothrin Solvent Used- Temperature, c '/ Precipitation Precipitation 1R, cis let's serial number weight 8 Volume of agent / solvent, ml reaction time, Sun weight g -S / 1S, cis-R content,% First 5.0 ethanol / 5.0 3/8 0.26 84.3 Second 10.0 n-propanol / 10.0 3/11 1.03 86.7 Third 50.0 n-propanol / 50.0 3/12, -10/4 then 8.7 91.9 4th 5.0 n-butanol / 5.0 3/33 0.14 86.9 5th 5.0 sec-butanolate / 5.0 3/8 0.41 82.6 6th 10.0 isobutanol / 10.0 3/11 1.18 79.0 7th 5.0 1: 1 tert-butanol ': isopropanol mixture / / 10.0 3/14 0.64 88.3 8th 10.0 isopropanol / 5.0 3/11 0.97 79.1 9th 5.0 n-pentanol; 3/33 0.64 68.8 10th 10.5 n-hexane / 10.0 0/9 0.61 99.1 11th 10.0 n-heptane / 10.0 3/22 0.48 98.6 12th 9.6 n-heptane / 10.0 3/11 0.73 96.5 13th 10.0 2,2,4-trimethylpentane / 10.0 3/8 1.17 80.3 14th 2000 n-hexane / 2000 0/18, -5/7 then 406 93.3 200.0 isopropanol / 200 0/7 26.5 ** 92.0 16th *** 204.0 isopropanol / 200 5/7 9.6 ** 97.0

* Recrystallized from petroleum ether (boiling range 40-60 ° C); after recrystallization 281 g of product are obtained ** Disregarding the weight of the seed crystal *** 4.0 g of seed crystal are added

Example 7

An oily concentrate

It is adjusted by mixing the components

produce a tumor of the following composition: oily concentrate agent 25.0% by weight Lubrol L. (Condensation of alkylphenol with ethylene oxide) Tuma) Calcium dodecylbenzene - 2.5 sulfonate 2.5 " Aromasol H (from alkylbenzenes stationary solvent mixture) 70.0 "

This concentrate, when diluted with water, can be easily converted into a spray formulation.

Example 8

An oily concentrate

By mixing the components, an oily concentrate of the following composition is prepared:

Active ingredient 25.0% by weight

Lubrol L 4.0

Calcium dodecyl benzene ⁶⁵ sulfonate 6.0

Aromasol H 65.0

Example 9

Wettable Powder Formulation By mixing the components, a wettable powder formulation is prepared having the following composition:

agent

Sodium silicate

Calcium ligninsulfonate

china clay

25.0% by weight 5.0 "

5.0 "

65.0 "

Example 10

A sprayable liquid formulation is mixed with 75% w / w xylene. A sprayable liquid formulation is obtained.

Example 11 Dusting agent% by weight mixed with 99% by weight talc. You're on plants

-6193185 yields a dusting agent that can be applied directly to other surfaces.

Example 12

The emulsifiable concentrate is mixed with 65% by weight xylene and 10% by weight Triton X-100 (alkylaryl polyether alcohol). An emulsifiable concentrate is obtained which is diluted with water before use. The diluted preparation can be used for agricultural purposes and for controlling domestic parasites (by external treatment).

Example 13

Particle weight of the active ingredient is mixed with 95 parts by weight of talc. We get a pollinator that can be used to control parasitic pathogens in domestic animals.

Example 14

Dispersible concentrate is mixed with 10 parts by weight of Lissapol NX (condensate of ethylene oxide with octylphenol) and 80 parts by weight of diacetone alcohol. The concentrate is dispersed in water before use. The dispersion thus obtained can be used as a spray for controlling insect pests.

Example 15

Emulsifiable concentrate

The components are mixed and the mixture is stirred until the components are completely dissolved. An emulsifiable concentrate is obtained having the following composition: Active ingredient 20.0% by weight

Lubrol L 17.0

Calcium dodecylbenzene sulfonate 3.0

Ethylene dichloride id 45.0

Aromasol H 15.0

Example 16

Dispersible powder formulation

By mixing the components, a powder composition which is easily dispersible in liquids is prepared as follows: Active ingredient 50.0% by weight

Dispersol T 5.0 ”%

China Porcelain 45.0

Example 17

Highly active preparation

90 parts by weight of the active ingredient are mixed with 10 parts by weight of xylene. The resulting high content formulation is diluted, if necessary, with paraffinic hydrocarbon diluents prior to application. The product is also effective when applied in very small volumes.

Example 18

Investigation of insecticidal activity

The activity of the insecticide produced according to the invention is shown in Table IV. of the known cyhalothrin (cis-3- / Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl / -2,2-dimethylcyclopropanecarboxylic acid35-a). cyano-3-phenoxybenzyl ester). The insects were treated with increasing concentrations of the active compound and the concentration of active ingredient needed to kill 50% of the insects (LD ₅₀ , ppm) was determined. The results are shown in Table IV. in Table.

ARC. spreadsheet

Insect

Chilo partellus (larvae) Heliothis virescens (larvae) Blattella germanica (adult Blattella germanica (puppet) Musca domestica (adult) Tetranychus urticae (mature Myzus persicae (all stages of development)

LD50, (a) pPM (B) Ratio of LD50 values (A) / (b) 3.57 1.20 2.98 3.56 1.61 2.21 26.64 13.01 2.05 49.34 18.24 2.71 0.83 0.36 2.30 64,40 30.05 2.14 3.82 1.91 2.00

(a) cy halothrin (b) the product of Example 3

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The IV. Table 2 shows that the activity of the isomeric mixture of two isomers produced according to the invention is at least twice that of the isomeric mixture of four isomers.

Claims (6)

PATENT CLAIMS A process for the preparation of crystalline structures of cis-3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid a- (1R, cis) -3- (Z2-Chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2, substantially free of other isoisomers of cyano-3-phenoxybenzyl ester dimethylcyclopropanecarboxylic acid (S) -α-cyano-3-phenoxybenzyl ester and (1S, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en- 1-yl) -2,2-dimethylcyclopropanecarboxylic acid - (R) -? - cyano-3-phenoxybenzyl ester in a 1: 1 molar ratio, characterized in that (i) (1R, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid (S) -α-cyano-3-phenoxybenzyl ester, (1R, cis) -3- (Z-2-Chloro-3,3,3, -trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid (R) -α-cyano-3 phenoxy benzyl ester, (1S, cis) -3- (Ζ-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid ( S) -α-cyano-3-phenoxybenzyl ester and (1S, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2 , 2- A solution of the solvent and solvent in a weight ratio of 2: 1 to 1: 5 is prepared from a mixture of (R) -α-cyano-3-phenoxybenzyl ester of dimethylcyclopropanecarboxylic acid with C2-C6 alkanol or C8-C8 liquid alkane. (ii) cooling the solution to -20 ° C to + 10 ° C and adding to the solution crystals of the enantiomeric pair to be separated in an amount of 0.5 to 25% by weight of the solute; (ii) separating the precipitated crystalline material from the solution in a known manner and (v) recrystallizing the resulting crystalline material, if desired, in one or more steps, until other cis-3- (Z) is present. -2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid acyano-3-phenoxybenzyl ester content 10 Not reduced to 5% or less by weight. (Priority: 10/10/1982) Process according to claim 1, characterized in that in step (i), the solute to solvent ratio is 1: 1 by weight. 10 solutions were prepared. (Priority: October 10, 1982) 3. The process of claim 1 wherein the solvent is isopropanol. (Priority: 10/10/1982) 15 The process according to claim 1, wherein in step (ii) 1.0 to 10% by weight of seed crystal is added to the solution. (Priority: 10/11/1982) The process according to claim 1, wherein in step (ii), seed crystals melting at a temperature above 47 ° C are added to the solution and in step (iv) A product with a melting point greater than 47 ° C is isolated. (Priority: March 28, 1983) An insecticidal composition comprising a crystalline active ingredient, a 30 cis-3- (Z-2-Chloro-3,3,3-trifluoro-prop-1-en-1-yl) -2,2-dimethyl-cyclopropanecarboxylic acid acyano-3-phenoxy-benzyl ester (R, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanoic acid, substantially free of other isomers (S) -acyano-3-phenoxybenzyl ester and (1S, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2 - Contains a 1: 1 molar mixture of dimethylcyclopropanecarboxylic acid (R) -α-cyano-3-phenoxybenzyl ester from 0.0001 to 95 In an amount of 40% by weight with an inert solid or liquid carrier or diluent, preferably talc, porcelain earth, ethylene chloride or hydrocarbon solvents and optionally one or more known surfactants, preferably calcium dodecylbenzene sulfonate, 11th